U.S. patent application number 15/497223 was filed with the patent office on 2017-08-10 for organic semiconductor element, manufacturing method thereof, compound, composition for forming organic semiconductor film, and organic semiconductor film.
The applicant listed for this patent is FUJIFILM CORPORATION. Invention is credited to Tetsu KITAMURA.
Application Number | 20170229655 15/497223 |
Document ID | / |
Family ID | 55954287 |
Filed Date | 2017-08-10 |
United States Patent
Application |
20170229655 |
Kind Code |
A1 |
KITAMURA; Tetsu |
August 10, 2017 |
ORGANIC SEMICONDUCTOR ELEMENT, MANUFACTURING METHOD THEREOF,
COMPOUND, COMPOSITION FOR FORMING ORGANIC SEMICONDUCTOR FILM, AND
ORGANIC SEMICONDUCTOR FILM
Abstract
An object of the invention is to provide an organic
semiconductor element having high mobility and excellent temporal
stability under high humidity, and a manufacturing method thereof.
Another object is to provide a novel compound suitable for an
organic semiconductor. Still another object is to provide an
organic semiconductor film having high mobility and excellent
temporal stability under high humidity and a composition for
forming an organic semiconductor film that can suitably form the
organic semiconductor film. The organic semiconductor element
according to the invention includes an organic semiconductor layer
containing an organic semiconductor having a repeating unit
represented by Formula 1. ##STR00001##
Inventors: |
KITAMURA; Tetsu; (Kanagawa,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM CORPORATION |
Tokyo |
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JP |
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|
Family ID: |
55954287 |
Appl. No.: |
15/497223 |
Filed: |
April 26, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/JP2015/081179 |
Nov 5, 2015 |
|
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15497223 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 61/125 20130101;
C08G 2261/228 20130101; C08G 2261/1412 20130101; C08G 2261/1452
20130101; C08G 2261/3243 20130101; C08G 2261/3223 20130101; C08G
2261/3241 20130101; H01L 51/05 20130101; C08G 2261/3221 20130101;
C08G 2261/148 20130101; H01L 51/0043 20130101; C08G 2261/3242
20130101; C08G 2261/314 20130101; C09D 165/00 20130101; C08G 61/126
20130101; C08G 2261/1428 20130101; C09D 165/00 20130101; H01L
51/0545 20130101; C08G 2261/1426 20130101; H01L 51/0035 20130101;
H01L 51/0541 20130101; C08G 2261/146 20130101; H01L 29/786
20130101; C08L 25/16 20130101; C08G 2261/18 20130101; C08G 61/12
20130101; C08G 2261/3225 20130101; C08G 2261/414 20130101; C08G
61/123 20130101; C08L 65/00 20130101; C08L 2205/02 20130101; C08G
2261/334 20130101; C08G 2261/312 20130101; H01L 51/0003 20130101;
H01L 51/0036 20130101; H01L 51/0558 20130101; C08G 2261/3244
20130101; C08G 2261/344 20130101; C08G 2261/141 20130101; C08G
2261/92 20130101; C08G 2261/124 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C08G 61/12 20060101 C08G061/12 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 14, 2014 |
JP |
2014-231214 |
Claims
1. An organic semiconductor element comprising: an organic
semiconductor layer containing an organic semiconductor having a
repeating unit represented by Formula 1, ##STR00023## in Formula 1,
X.sup.11 and X.sup.12 each independently represent any one of
CH.sub.2, CR.sup.11.sub.2, O, S, Se, and SiR.sup.11.sub.2,
R.sup.11's each independently represent a monovalent organic group,
Y.sup.11 and Y.sup.12 each independently represent O, S, N--CN, or
CQ.sub.2, Q represents CN, CF.sub.3, C(.dbd.O)R.sup.12,
C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12, R.sup.12's each
independently represent a monovalent organic group, a plurality of
R.sup.12's may be bonded to each other to form a ring, Ar.sup.11,
Ar.sup.12, and Ar.sup.13 each independently represent an aromatic
hydrocarbon group, an aromatic heterocyclic group, a vinylene
group, or an ethynylene group, m11 represents an integer of 0 to 2,
m12 represents an integer of 0 to 4, and m13 represents an integer
of 0 to 2.
2. The organic semiconductor element according to claim 1, wherein
both of X.sup.11 and X.sup.12 are O or S.
3. The organic semiconductor element according to claim 1, wherein
both of Y.sup.11 and Y.sup.12 are O or S.
4. The organic semiconductor element according to claim 1, wherein
the repeating unit represented by Formula 1 is a repeating unit
represented by Formula 2, ##STR00024## in Formula 2, X.sup.11 and
X.sup.12 each independently represent any one of CH.sub.2,
CR.sup.11.sub.2, O, S, Se, and SiR.sup.11.sub.2, R.sup.11's each
independently represent a monovalent organic group, Y.sup.11 and
Y.sup.12 each independently represent O, S, N--CN, or CQ.sub.2, Q
represents CN, CF.sub.3, C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or
SO.sub.2R.sup.12, R.sup.12's each independently represent a
monovalent organic group, a plurality of R.sup.12's may be bonded
to each other to form a ring, Ar.sup.12 represents an aromatic
hydrocarbon group, an aromatic heterocyclic group, a vinylene
group, or an ethynylene group, m12 represents an integer of 0 to 4,
X.sup.21 and X.sup.22 each independently represent any one of
CH.sub.2, CR.sup.11'.sub.2, O, S, Se, and SiR.sup.11'.sub.2,
R.sup.11''s each independently represent a hydrogen atom or a
monovalent organic group, R.sup.21 to R.sup.24 each independently
represent a hydrogen atom or a monovalent organic group, m11'
represents an integer of 0 to 2, and m13' represents an integer of
0 to 2.
5. A compound comprising: a repeating unit represented by Formula
1, ##STR00025## in Formula 1, X.sup.11 and X.sup.12 each
independently represent any one of CH.sub.2, CR.sup.11.sub.2, O, S,
Se, and SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
6. The compound according to claim 5, wherein both of X.sup.11 and
X.sup.12 are O or S.
7. The compound according to claim 5, wherein both of Y.sup.11 and
Y.sup.12 are O or S.
8. The compound according to claim 5, wherein the repeating unit
represented by Formula 1 is a repeating unit represented by Formula
2, ##STR00026## in Formula 2, X.sup.11 and X.sup.12 each
independently represent any one of CH.sub.2, CR.sup.11.sub.2, O, S,
Se, and SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.12 represents an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m12 represents an integer of 0 to 4, X.sup.21 and X.sup.22
each independently represent any one of CH.sub.2, CR.sup.11'.sub.2,
O, S, Se, and SiR.sup.11'.sub.2, R.sup.11's each independently
represent a hydrogen atom or a monovalent organic group, R.sup.21
to R.sup.24 each independently represent a hydrogen atom or a
monovalent organic group, m11' represents an integer of 0 to 2, and
m13' represents an integer of 0 to 2.
9. The compound according to claim 5, which is an organic
semiconductor.
10. A composition for forming an organic semiconductor film,
comprising: a compound having a repeating unit represented by
Formula 1; and a solvent, ##STR00027## in Formula 1, X.sup.11 and
X.sup.12 each independently represent any one of CH.sub.2,
CR.sup.11.sub.2, O, S, Se, and SiR.sup.11.sub.2, R.sup.11's each
independently represent a monovalent organic group, Y.sup.11 and
Y.sup.12 each independently represent O, S, N--CN, or CQ.sub.2, Q
represents CN, CF.sub.3, C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or
SO.sub.2R.sup.12, R.sup.12's each independently represent a
monovalent organic group, a plurality of R.sup.12's may be bonded
to each other to form a ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13
each independently represent an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m11 represents an integer of 0 to 2, m12 represents an
integer of 0 to 4, and m13 represents an integer of 0 to 2.
11. The composition for forming an organic semiconductor film
according to claim 10, wherein both of X.sup.11 and X.sup.12 are O
or S.
12. The composition for forming an organic semiconductor film
according to claim 10, wherein both of Y.sup.11 and Y.sup.12 are O
or S.
13. The composition for forming an organic semiconductor film
according to claim 10, wherein the repeating unit represented by
Formula 1 is a repeating unit represented by Formula 2,
##STR00028## in Formula 2, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.12 represents an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m12 represents an integer of 0 to 4, X.sup.21 and X.sup.22
each independently represent any one of CH.sub.2, CR.sup.11'.sub.2,
O, S, Se, and SiR.sup.11'.sub.2, R.sup.11's each independently
represent a hydrogen atom or a monovalent organic group, R.sup.21
to R.sup.24 each independently represent a hydrogen atom or a
monovalent organic group, m11' represents an integer of 0 to 2, and
m13' represents an integer of 0 to 2.
14. The composition for forming an organic semiconductor film
according to claim 10, further comprising: a binder polymer.
15. A method of manufacturing an organic semiconductor element,
comprising: a coating step of coating a substrate with the
composition for forming an organic semiconductor film according to
claim 10.
16. An organic semiconductor film comprising: a compound having a
repeating unit represented by Formula 1, ##STR00029## in Formula 1,
X.sup.11 and X.sup.12 each independently represent any one of
CH.sub.2, CR.sup.11.sub.2, O, S, Se, and SiR.sup.11.sub.2,
R.sup.11's each independently represent a monovalent organic group,
Y.sup.11 and Y.sup.12 each independently represent O, S, N--CN, or
CQ.sub.2, Q represents CN, CF.sub.3, C(.dbd.O)R.sup.12,
C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12, R.sup.12's each
independently represent a monovalent organic group, a plurality of
R.sup.12's may be bonded to each other to form a ring, Ar.sup.11,
Ar.sup.12, and Ar.sup.13 each independently represent an aromatic
hydrocarbon group, an aromatic heterocyclic group, a vinylene
group, or an ethynylene group, m11 represents an integer of 0 to 2,
m12 represents an integer of 0 to 4, and m13 represents an integer
of 0 to 2.
17. The organic semiconductor film according to claim 16, wherein
both of X.sup.11 and X.sup.12 are O or S.
18. The organic semiconductor film according to claim 16, wherein
both of Y.sup.11 and Y.sup.12 are O or S.
19. The organic semiconductor film according to claim 16, wherein
the repeating unit represented by Formula 1 is a repeating unit
represented by Formula 2, ##STR00030## in Formula 2, X.sup.11 and
X.sup.12 each independently represent any one of CH.sub.2,
CR.sup.11.sub.2, O, S, Se, and SiR.sup.11.sub.2, R.sup.11's each
independently represent a monovalent organic group, Y.sup.11 and
Y.sup.12 each independently represent O, S, N--CN, or CQ.sub.2, Q
represents CN, CF.sub.3, C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or
SO.sub.2R.sup.12, R.sup.12's each independently represent a
monovalent organic group, a plurality of R.sup.12's may be bonded
to each other to form a ring, Ar.sup.12 represents an aromatic
hydrocarbon group, an aromatic heterocyclic group, a vinylene
group, or an ethynylene group, m12 represents an integer of 0 to 4,
X.sup.21 and X.sup.22 each independently represent any one of
CH.sub.2, CR.sup.11'.sub.2, O, S, Se, and SiR.sup.11'.sub.2,
R.sup.11''s each independently represent a hydrogen atom or a
monovalent organic group, R.sup.21 to R.sup.24 each independently
represent a hydrogen atom or a monovalent organic group, m11'
represents an integer of 0 to 2, and m13' represents an integer of
0 to 2.
20. The organic semiconductor film according to claim 16, which is
manufactured by a solution coating method.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation application of
International Application No. PCT/JP2015/081179, filed Nov. 5,
2015, the disclosure of which is incorporated herein by reference
in its entirety. Further, this application claims priority from
Japanese Patent Application No. 2014-231214, filed Nov. 14, 2014,
the disclosure of which is incorporated herein by reference in its
entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to an organic semiconductor element, a
manufacturing method thereof, a compound, a composition for forming
an organic semiconductor film, and an organic semiconductor
film.
[0004] 2. Description of the Related Art
[0005] An organic transistor having an organic semiconductor film
(organic semiconductor layer) is used in a field effect transistor
(FET) used in a liquid crystal display or an organic EL display,
RFID (RF tag), and the like, because lightening of weight, cost
reduction and flexibilization can be achieved.
[0006] As the organic semiconductor in the related art, those
disclosed in JP2007-516315A and JP2014-514413A are known.
SUMMARY OF THE INVENTION
[0007] An object to be achieved by the present invention is to
provide an organic semiconductor element having high mobility and
excellent temporal stability under high humidity, and a
manufacturing method thereof.
[0008] Another object to be achieved by the present invention is to
provide a novel compound which is suitable as an organic
semiconductor.
[0009] Still another object to be achieved by the present invention
is to provide an organic semiconductor film having high mobility
and excellent temporal stability under high humidity and a
composition for forming an organic semiconductor film that can
suitably form the organic semiconductor film.
[0010] The objects of the invention were solved by the means
described in <1>, <5>, <10>, <15>, or
<16> below. <2> to <4>, <6> to <9>,
<11> to <14>, and <17> to <20> which are
preferable embodiments are also described below.
[0011] <1> An organic semiconductor element comprising:
[0012] an organic semiconductor layer containing an organic
semiconductor having a repeating unit represented by Formula 1,
##STR00002##
[0013] in Formula 1, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
[0014] <2> The organic semiconductor element according to
<1>, in which both of X.sup.11 and X.sup.12 are O or S.
[0015] <3> The organic semiconductor element according to
<1> or <2>, in which both of Y.sup.11 and Y.sup.12 are
O or S.
[0016] <4> The organic semiconductor element according to any
one of <1> to <3>, in which the repeating unit
represented by Formula 1 is a repeating unit represented by Formula
2,
##STR00003##
[0017] in Formula 2, X.sup.1 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.12 represents an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m12 represents an integer of 0 to 4, X.sup.21 and X.sup.22
each independently represent any one of CH.sub.2, CR.sup.11'.sub.2,
O, S, Se, and SiR.sup.11'.sub.2, R.sup.11''s each independently
represent a hydrogen atom or a monovalent organic group, R.sup.21
to R.sup.24 each independently represent a hydrogen atom or a
monovalent organic group, m11' represents an integer of 0 to 2, and
m13' represents an integer of 0 to 2.
[0018] <5> A compound comprising: a repeating unit
represented by Formula 1,
##STR00004##
[0019] in Formula 1, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
[0020] <6> The compound according to <5>, in which both
of X.sup.11 and X.sup.12 are O or S.
[0021] <7> The compound according to <5> or <6>,
in which both of Y.sup.11 and Y.sup.12 are O or S.
[0022] <8> The compound according to any one of <5> to
<7>, in which the repeating unit represented by Formula 1 is
a repeating unit represented by Formula 2,
##STR00005##
[0023] in Formula 2, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.12 represents an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m12 represents an integer of 0 to 4, X.sup.21 and X.sup.22
each independently represent any one of CH.sub.2, CR.sup.11'.sub.2,
O, S, Se, and SiR.sup.11'.sub.2, R.sup.11's each independently
represent a hydrogen atom or a monovalent organic group, R.sup.21
to R.sup.24 each independently represent a hydrogen atom or a
monovalent organic group, m11' represents an integer of 0 to 2, and
m13' represents an integer of 0 to 2.
[0024] <9> The compound according to any one of <5> to
<8>, which is an organic semiconductor.
[0025] <10> A composition for forming an organic
semiconductor film, comprising: a compound having a repeating unit
represented by Formula 1; and a solvent,
##STR00006##
[0026] in Formula 1, X.sup.1 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
[0027] <11> The composition for forming an organic
semiconductor film according to <10>, in which both of
X.sup.11 and X.sup.12 are O or S.
[0028] <12> The composition for forming an organic
semiconductor film according to <10> or <11>, in which
both of Y.sup.11 and Y.sup.12 are O or S.
[0029] <13> The composition for forming an organic
semiconductor film according to any one of <10> to
<12>, in which the repeating unit represented by Formula 1 is
a repeating unit represented by Formula 2,
##STR00007##
[0030] in Formula 2, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.12 represents an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m12 represents an integer of 0 to 4, X.sup.21 and X.sup.22
each independently represent any one of CH.sub.2, CR.sup.11'.sub.2,
O, S, Se, and SiR.sup.11'.sub.2, R.sup.11's each independently
represent a hydrogen atom or a monovalent organic group, R.sup.21
to R.sup.24 each independently represent a hydrogen atom or a
monovalent organic group, m11' represents an integer of 0 to 2, and
m13' represents an integer of 0 to 2.
[0031] <14> The composition for forming an organic
semiconductor film according to any one of <10> to
<13>, further comprising: a binder polymer.
[0032] <15> A method of manufacturing an organic
semiconductor element, comprising: a coating step of coating a
substrate with the composition for forming an organic semiconductor
film according to any one of <10> to <14>.
[0033] <16> An organic semiconductor film comprising: a
compound having a repeating unit represented by Formula 1,
##STR00008##
[0034] in Formula 1, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
[0035] <17> The organic semiconductor film according to
<16>, in which both of X.sup.11 and X.sup.12 are O or S.
[0036] <18> The organic semiconductor film according to
<16> or <17>, in which both of Y.sup.11 and Y.sup.12
are O or S.
[0037] <19> The organic semiconductor film according to any
one of <16> to <18>, in which the repeating unit
represented by Formula 1 is a repeating unit represented by Formula
2,
##STR00009##
[0038] in Formula 2, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.12 represents an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group, m12 represents an integer of 0 to 4, X.sup.21 and X.sup.22
each independently represent any one of CH.sub.2, CR.sup.11'.sub.2,
O, S, Se, or SiR.sup.11'.sub.2, R.sup.11's each independently
represent a hydrogen atom or a monovalent organic group, R.sup.21
to R.sup.24 each independently represent a hydrogen atom or a
monovalent organic group, m11' represents an integer of 0 to 2, and
m13' represents an integer of 0 to 2.
[0039] <20> The organic semiconductor film according to any
one of <16> to <19>, which is manufactured by a
solution coating method.
[0040] According to the present invention, it is possible to
provide an organic semiconductor element having high mobility and
excellent temporal stability under high humidity and a
manufacturing method thereof.
[0041] According to the present invention, it is possible to
provide a novel compound suitable for an organic semiconductor.
[0042] According to the present invention, it is possible to
provide an organic semiconductor film having high mobility and
excellent temporal stability under high humidity and a composition
for forming an organic semiconductor film that can suitably form
the organic semiconductor film.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a schematic cross-sectional view of an aspect of
an organic semiconductor element of the present invention.
[0044] FIG. 2 is a schematic cross-sectional view of another aspect
of the organic semiconductor element of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] Hereinafter, the contents of the present invention will be
specifically described. The constituents in the following
description will be explained based on typical embodiments of the
present invention, but the present invention is not limited to the
embodiments. In the specification of the present application, "to"
is used to mean that the numerical values listed before and after
"to" are a lower limit and an upper limit respectively.
Furthermore, in the present invention, an organic EL element refers
to an organic electroluminescence element.
[0046] In the present specification, in a case where there is no
description regarding whether a group (atomic group) is substituted
or unsubstituted, the group includes both of a group having a
substituent and a group not having a substituent. For example, an
"alkyl group" includes not only an alkyl group not having a
substituent (unsubstituted alkyl group) but also an alkyl group
having a substituent (substituted alkyl group).
[0047] In the present specification, in some cases, a chemical
structural formula is described as a simplified structural formula
in which a hydrogen atom is omitted.
[0048] In the present invention, "mass %" and "weight %" have the
same definition, and "part by mass" and "part by weight" have the
same definition.
[0049] In the present invention, a combination of two or more
preferred aspects is more preferable.
[0050] (Organic Semiconductor Element)
[0051] The organic semiconductor element according to the present
invention has an organic semiconductor layer containing an organic
semiconductor (hereinafter, also referred to as a "specific organic
semiconductor compound") that has a repeating unit represented by
Formula 1.
[0052] As a result of diligent research, the present inventors
found that, if the specific organic semiconductor compound was
contained, the obtained organic semiconductor element or the
obtained organic semiconductor film had high mobility and excellent
temporal stability under high humidity, so as to complete the
present invention.
[0053] The detailed mechanism of exhibiting the effects is not
clear, but it is considered that the specific organic semiconductor
compound causes the film quality to be even, and thus temporal
stability under high humidity becomes excellent.
[0054] <Specific Organic Semiconductor Compound>
[0055] In the present invention, the specific organic semiconductor
compound has a repeating unit represented by Formula 1 below.
##STR00010##
[0056] In Formula 1, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.13's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
[0057] The specific organic semiconductor compound according to the
present invention is a novel compound.
[0058] The specific organic semiconductor compound according to the
present invention can be suitably used in an organic semiconductor
element, an organic semiconductor film, and a composition for
forming an organic semiconductor film.
[0059] In Formula 1, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2. It is preferable that X.sup.11 and X.sup.12 each
independently represent O or S, both of X.sup.11 and X.sup.12 are O
or S, and it is more preferable that both of X.sup.11 and X.sup.12
are S.
[0060] X.sup.11 and X.sup.12 may be different from each other. In
view of manufacturing suitability, it is preferable that X.sup.11
and X.sup.12 are the same with each other.
[0061] R.sup.11's each independently and preferably represent a
monovalent organic group, an alkyl group, or an aryl group, more
preferably an alkyl group having 1 to 20 carbon atoms and an aryl
group having 6 to 20 carbon atoms, and even more preferably an
alkyl group having 6 to 20 carbon atoms or a phenyl group. The
alkyl group may have any one of a linear shape, a branched shape,
and a cyclic shape.
[0062] Y.sup.11 and Y.sup.12 each independently represent O, S,
N--CN, or CQ.sub.2, Q represents CN, CF.sub.3, C(.dbd.O)R.sup.12,
C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12. It is preferable that
Y.sup.11 and Y.sup.12 each independently represent O or S, it is
more preferable that both of Y.sup.11 and Y.sup.12 are O or S, and
it is even more preferable that both of Y.sup.11 and Y.sup.12 are
S.
[0063] R.sup.12's each independently and preferably represent a
monovalent organic group, an alkyl group, or an aryl group, more
preferably an alkyl group having 1 to 20 carbon atoms and an aryl
group having 6 to 20 carbon atoms, even more preferably an alkyl
group having 1 to 20 carbon atoms, and particularly preferably an
alkyl group having 6 to 20 carbon atoms. The alkyl group may be any
one of a linear shape, a branched shape, and a cyclic shape.
[0064] A plurality of R.sup.12's may be bonded to each other to
form a ring. The ring formed with the plurality of R.sup.12 may be
further fused with an aromatic ring such as a benzene ring.
[0065] Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group.
[0066] Ar.sup.11 and Ar.sup.13 are preferably an aromatic
hydrocarbon group or an aromatic heterocyclic group. Ar.sup.11 and
Ar.sup.13 may have a polycyclic structure but are preferably a
monocyclic structure.
[0067] The aromatic hydrocarbon group is preferably an arylene
group having 6 to 20 carbon atoms and more preferably a phenylene
group or a naphthylene group.
[0068] The heteroatoms of the aromatic hetero ring are not
particularly limited. However, examples thereof include S, O, N,
and Se. Examples of the aromatic heterocyclic group include groups
obtained by removing two hydrogen atoms from a ring selected from
the group consisting of a thiophene ring, a furan ring, a pyran
ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a
pyrimidine ring, a pyridazine ring, a selenophene ring, an
imidazole ring, and a thienothiophene ring. A group obtained by
removing two hydrogen atoms from a ring selected from the group
consisting of a thiophene ring, a furan ring, a pyrrole ring, a
pyridine ring, a selenophene ring, and a thienothiophene ring is
preferable, and a group obtained by removing two hydrogen atoms
from a thiophene ring is more preferable.
[0069] An aromatic hydrocarbon group or an aromatic heterocyclic
group may have a substituent. Examples of the preferable
substituent include an alkyl group. An alkyl group having 1 to 20
carbon atoms is preferable, and an alkyl group having 8 to 20
carbon atoms is more preferable.
[0070] In view of manufacturing suitability, it is preferable that
Ar.sup.11 and Ar.sup.13 may be the same with each other.
[0071] Ar.sup.12 represent an aromatic hydrocarbon group, an
aromatic heterocyclic group, a vinylene group, or an ethynylene
group. A fused polycyclic aromatic group, a vinylene group, or a
thienylene group is preferable.
[0072] The aromatic hydrocarbon group is preferably an arylene
group having 6 to 20 carbon atoms and more preferably a group
obtained by removing one hydrogen atom from a ring selected from
the group consisting of a benzene ring, a naphthalene ring, an
anthracene ring, and a pyrene ring.
[0073] The heteroatom of the aromatic hetero ring is not
particularly limited, and examples thereof include S, O, N, Se, and
Si. Examples of the aromatic heterocyclic group include a group
obtained by removing two hydrogen atoms from a ring selected from
the group consisting of a thiophene ring, a furan ring, a pyran
ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a
pyrimidine ring, a pyridazine ring, a selenophene ring, an
imidazole ring, and a thienothiophene ring. The aromatic
heterocyclic group is preferably a group obtained by removing two
hydrogen atoms from a ring selected from the group consisting of a
thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, a
selenophene ring, and a thienothiophene ring, more preferably a
group obtained by removing two hydrogen atoms from a ring selected
from the group consisting of a thiophene ring and a thienothiophene
ring, and even more preferably a group obtained by removing two
hydrogen atoms from a thiophene ring.
[0074] The aromatic hydrocarbon group or the aromatic heterocyclic
group each may have a substituent. Examples of the preferable
substituent include an alkyl group, and the preferable substituent
is preferably an alkyl group having 1 to 20 carbon atoms and more
preferably an alkyl group of 8 to 20 carbon atoms.
[0075] Ar.sup.12 preferably represents a fused polycyclic aromatic
group in which a plurality of aromatic hydrocarbon groups or a
plurality of aromatic heterocyclic groups are fused. In a case
where Ar.sup.12 represents a fused polycyclic aromatic group, a
fused ring having three to seven rings is preferable, and a fused
ring having three to five rings is more preferable. In the fused
ring, a non-aromatic heterocyclic group such as cyclotetramethylene
silane may be included.
[0076] In a case where Ar.sup.12 represents a fused polycyclic
aromatic group, a structure represented by any one of Formula AR-1
to AR-10 below is preferable.
##STR00011## ##STR00012##
[0077] In Formulae AR-1 to AR-10, X.sup.A1, X.sup.A2, X.sup.A4, and
X.sup.A5 each independently represent any one of S, O,
CR.sup.AR.sub.2, NR.sup.AR, and SiR.sup.AR.sub.2, and R.sup.AR's
each independently represent a monovalent organic group. R.sup.AR
is preferably an alkyl group having 8 to 20 carbon atoms.
[0078] Among these, AR-1 to AR-6, AR-9, or AR-10 is preferable, any
one of AR-1 to AR-5 is more preferable, and AR-1 or AR-5 is even
more preferable.
[0079] The polycyclic aromatic hydrocarbon group or the polycyclic
aromatic heterocyclic group may have a substituent. Examples of the
preferable substituent include an alkyl group, an alkyl group
having 1 to 30 carbon atoms is preferable and an alkyl group having
8 to 20 carbon atoms is more preferable.
[0080] m11 preferably represents an integer of 0 to 2, m12
represents an integer of 0 to 4, m13 represents an integer of 0 to
2, and a sum of m11, m12, and m13 is preferably 1 or greater.
[0081] In a case where Ar.sup.12 is a vinylene group or an
ethynylene group, m12 preferably represent 1, and m11 and m13 each
independently and preferably represent 1 or 2.
[0082] In a case where Ar.sup.12 is an aromatic hydrocarbon group
or an aromatic heterocyclic group, m12 is preferably 1 or 2, m11
and m13 each independently represent and preferably 0 or 1.
[0083] In a case where Ar.sup.12 is a fused polycyclic aromatic
group, m12 is preferably 1, m11 and m13 each independently and
preferably represent 0 or 1.
[0084] The repeating unit represented by Formula 1 is preferably a
repeating unit represented by Formula 2.
##STR00013##
[0085] In Formula 2, X.sup.11, X.sup.12, Y.sup.11, Y.sup.12,
Ar.sup.12, and m12 are respectively the same as X.sup.11, X.sup.12,
Y.sup.11, Y.sup.12, Ar.sup.12, and m12 in Formula 1, the preferably
ranges thereof are also the same, X.sup.21 and X.sup.22 each
independently represent any one of CH.sub.2, CR.sup.11.sub.2, O, S,
Se, and SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, R.sup.21 to R.sup.24 each independently
represent a hydrogen atom or a monovalent organic group, m11'
represents an integer of 0 to 2, and m13' represents an integer of
0 to 2.
[0086] X.sup.21 and X.sup.22 each independently represent any one
of O, S, Se, NR.sup.12', and SiR.sup.12'.sub.2, any one of O, S,
and NR.sup.12' are more preferable, and S is even more
preferable.
[0087] R.sup.12's each independently represent a hydrogen atom or a
monovalent organic group, an alkyl group is preferable, an alkyl
group having 1 to 30 carbon atoms is more preferable, and an alkyl
group having 1 to 15 carbon atoms is even more preferable. The
alkyl group may be any one of a linear shape, a branched shape, and
a cyclic shape.
[0088] R.sup.21 to R.sup.24 each independently represent a hydrogen
atom or a monovalent organic group, an alkyl group having 1 to 20
carbon atoms is preferable, and an alkyl group having 8 to 20
carbon atoms is more preferable.
[0089] m11' represents an integer of 0 to 2, m13' represents an
integer of 0 to 2, and a sum of m11', m12, and m13' is preferably 1
or greater.
[0090] In a case where Ar.sup.12 is a vinylene group or an
ethynylene group, m12 represents 1, m11' and m13' each
independently represent and preferably 1 or 2.
[0091] In a case where Ar.sup.12 is an aromatic hydrocarbon group
or an aromatic heterocyclic group, m12 is preferably 1 or 2, m11'
and m13' each independently represent and preferably 0 or 1.
[0092] In a case where Ar.sup.12 is a fused polycyclic aromatic
group, m12 is preferably 1, m11' and m13' each independently and
preferably represent 0 or 1.
[0093] In the specific organic semiconductor compound, the content
of the repeating unit represented by Formula 1 is preferably 60 to
100 mass %, more preferably 80 to 100 mass %, and even more
preferably 90 to 100 mass % with respect to a total mass of the
specific organic semiconductor compound.
[0094] The weight-average molecular weight of the specific organic
semiconductor compound is not particularly limited, but the
weight-average molecular weight is preferably 1,000 to 2,000,000,
more preferably 10,000 to 1,000,000, and even more preferably
50,000 to 500,000.
[0095] If the molecular weight is in the range described above, it
is possible to cause solubility to the solvent and the film quality
stability to be compatible with each other.
[0096] According to the present invention, a weight-average
molecular weight and a number-average molecular weight are measured
by a gel permeation chromatography method (GPC method) and can be
obtained in terms of standard polystyrene. Specifically, for
example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as
GPC, three of TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, TSKgeL
SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mmID.times.15
cm) are used as columns, and THF (tetrahydrofuran) is used as an
eluent. As the condition, the sample concentration is set as 0.35
mass %, a flow rate is set as 0.35 ml/min, a sample injection
volume is set as 10 .mu.l, a measurement temperature is set as
40.degree. C., and an IR detector was used. A calibration curve is
manufactured from eight samples of "standard sample TSK standard,
polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500",
"A-1000", and "n-propylbenzene" manufactured by Tosoh
Corporation.
[0097] In an organic semiconductor layer described below, and an
organic semiconductor film or a composition for forming an organic
semiconductor film described below, only one specific organic
semiconductor compound may be included, and two or more types of
the specific organic semiconductor compounds may be included.
However, in view of alignment, only one type is preferable.
[0098] Specific examples of the specific organic semiconductor
compound represented by Formula 1 used in the present invention
preferably include compounds (E-1 to E-22 and E-25) containing
repeating units below, but the present invention is not limited
thereto.
##STR00014## ##STR00015## ##STR00016## ##STR00017##
##STR00018##
[0099] Among these, E-1 to E-4, E-6, E-9, E-12, E-13, and E-15 are
preferable, and E-4, E-6, E-12, E-13, and E-15 are more
preferable.
[0100] The synthesis method of the specific organic semiconductor
compound is not particularly limited, and the specific organic
semiconductor compound can be synthesized in the well-known
methods. For example, the synthesis can be performed with reference
to JP2011-168747A, Macromol., 2013, 46, 3887., and J. Org. Chem.
1985, 50, 1681.
[0101] In the organic semiconductor layer of the organic
semiconductor element according to the present invention and the
organic semiconductor film according to the present invention
described below, the content of the specific organic semiconductor
compound is preferably 30 to 100 mass %, more preferably 50 to 100
mass %, and even more preferably 70 to 100 mass % with respect to a
total mass of the organic semiconductor layer or the organic
semiconductor film. In a case where a binder polymer described
below is not contained, the content is preferably 90 to 100 mass %
and more preferably 95 to 100 mass % with respect to a total mass
of the organic semiconductor layer or the organic semiconductor
film.
[0102] (Compound)
[0103] The compound according to the present invention has a
repeating unit represented by Formula 1.
##STR00019##
[0104] In Formula 1, X.sup.11 and X.sup.12 each independently
represent any one of CH.sub.2, CR.sup.11.sub.2, O, S, Se, and
SiR.sup.11.sub.2, R.sup.11's each independently represent a
monovalent organic group, Y.sup.11 and Y.sup.12 each independently
represent O, S, N--CN, or CQ.sub.2, Q represents CN, CF.sub.3,
C(.dbd.O)R.sup.12, C(.dbd.O)OR.sup.12, or SO.sub.2R.sup.12,
R.sup.12's each independently represent a monovalent organic group,
a plurality of R.sup.12's may be bonded to each other to form a
ring, Ar.sup.11, Ar.sup.12, and Ar.sup.13 each independently
represent an aromatic hydrocarbon group, an aromatic heterocyclic
group, a vinylene group, or an ethynylene group, m11 represents an
integer of 0 to 2, m12 represents an integer of 0 to 4, and m13
represents an integer of 0 to 2.
[0105] In Formula 1, X.sup.11, X.sup.12, Y.sup.11, Y.sup.12, Ar,
Ar.sup.12, Ar.sup.13, m11, m12, and m13 respectively have the same
meaning as X.sup.11, X.sup.12, Y.sup.11, Y.sup.12, Ar.sup.11,
Ar.sup.12, Ar.sup.13, m11, m12, and m13 in the specific organic
semiconductor compound, and preferable aspects thereof are also the
same.
[0106] The compound according to the present invention is
preferably an organic semiconductor compound.
[0107] The content, the weight-average molecular weight, the
specific examples, and the synthesis methods of the repeating unit
represented by Formula 1 in compound according to the present
invention are the same as those in the specific organic
semiconductor compound, and preferably aspects thereof are also the
same.
[0108] <Binder Polymer>
[0109] The organic semiconductor layer of the organic semiconductor
element according to the present invention preferably contains the
binder polymer.
[0110] The organic semiconductor element according to the present
invention may be an organic semiconductor element having a layer
including the organic semiconductor layer and the binder
polymer.
[0111] The types of the binder polymer are not particularly
limited, and well-known binder polymers can be used.
[0112] Examples of the binder polymer includes insulating polymers
such as polystyrene, polycarbonate, polyarylate, polyester,
polyamide, polyimide, polyurethane, polysiloxane, polysulfone,
polymethyl methacrylate, polymethyl acrylate, cellulose,
polyethylene, and polypropylene, and copolymers thereof, a
semiconductor polymer such as polysilane, polycarbazole,
polyarylamine, polyfluorene, polythiophene, polypyrrole,
polyaniline, polyparaphenylenevinylene, polyacene, and
polyheteroacene, and copolymers thereof, and rubber, and a
thermoplastic elastomer.
[0113] Among these, as the binder polymer, a polymer compound (a
polymer having a monomer unit having a benzene ring group) having a
benzene ring is preferable. The content of the monomer unit having
a benzene ring group is not particularly limited. However, the
content is preferably 50 mol % or greater, more preferably 70 mol %
or greater, and even more preferably 90 mol % or greater with
respect to the entire monomer unit. The upper limit is not
particularly limited, but examples of the upper limit include 100
mol %.
[0114] Examples of the binder polymer include polystyrene,
poly(.alpha.-methylstyrene), polyvinyl cinnamate,
poly(4-vinylphenyl), poly(4-methylstyrene), poly[bis(4-phenyl)
(2,4,6-trimethylphenyl)amine], and
poly[2,6-(4,4-bis(2-ethylhexyl)-4H
cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)],
and poly(.alpha.-methylstyrene) is particularly preferable.
[0115] A weight-average molecular weight of the binder polymer is
not particularly limited, but is preferably 1,000 to 2,000,000,
more preferably 3,000 to 1,000,000, and even more preferably 5,000
to 600,000.
[0116] In a case where a solvent described below is used, it is
preferable that the binder polymer exhibits solubility higher than
the solubility of the specific organic semiconductor compound in a
used solvent. If the above aspect is adopted, mobility and heat
stability of the obtained organic semiconductor are further
improved.
[0117] A content of the binder polymer in the organic semiconductor
layer of the organic semiconductor element of the present invention
is preferably 1 to 200 parts by mass, more preferably 10 to 150
parts by mass, and even more preferably 20 to 120 parts by mass
with respect to 100 parts by mass of the content of the specific
organic semiconductor compound. If the content is within the above
range, mobility and heat stability of the obtained organic
semiconductor are further improved.
[0118] <Other Components>
[0119] Other components may be included other than the specific
organic semiconductor compound and the binder polymer may be
included in the organic semiconductor layer according to the
organic semiconductor element of the present invention.
[0120] As other components, well-known additives and the like can
be used.
[0121] In the organic semiconductor layer of the present invention,
a content of the components other than the specific organic
semiconductor compound and the binder polymer is preferably 10 mass
% or less, more preferably 5 mass % or less, even more preferably 1
mass % or less, and particularly preferably 0.1 mass % or less with
respect to the total mass of the organic semiconductor layer. If
the content of other components is within the above range, film
formability is improved, and mobility and heat stability of the
obtained organic semiconductor are further improved.
[0122] The method of forming the organic semiconductor layer
according to the organic semiconductor element of the present
invention is not particularly limited. However, a desired organic
semiconductor layer can be formed by applying the composition for
forming the organic semiconductor film according to the present
invention described below to a source electrode, a drain electrode,
and a gate insulating film and performing a drying treatment, if
necessary.
[0123] The organic semiconductor element of the present invention
is preferably manufactured using the composition for forming an
organic semiconductor film of the present invention described
below.
[0124] A method of manufacturing an organic semiconductor film or
an organic semiconductor element by using the composition for
forming an organic semiconductor film of the present invention is
not particularly limited, and known methods can be adopted.
Examples thereof include a method (also referred to as "solution
coating method") of manufacturing an organic semiconductor film by
applying the composition onto a predetermined base material and if
necessary, performing a drying treatment.
[0125] The method of applying the composition onto a base material
is not particularly limited, and known methods can be adopted.
Examples thereof include an ink jet printing method, a flexographic
printing method, a bar coating method, a spin coating method, a
knife coating method, a doctor blade method, and the like. Among
these, an ink jet printing method, and a flexographic printing
method are preferable.
[0126] Preferred examples of the flexographic printing method
include an aspect in which a photosensitive resin plate is used as
a flexographic printing plate. By printing the composition onto a
substrate according to the aspect, a pattern can be easily
formed.
[0127] Among the above methods, the method of manufacturing an
organic semiconductor element of the present invention preferably
includes a coating step of coating a substrate with the composition
for forming an organic semiconductor film of the present invention
and more preferably includes a coating step of causing the
composition for forming an organic semiconductor film of the
present invention to include a solvent, coating a substrate with
the composition for forming an organic semiconductor film of the
present invention, and a removing step of removing the solvent from
the composition with which the substrate is coated.
[0128] The composition for forming the organic semiconductor film
according to the present invention described below preferably
includes a solvent and more preferably includes an organic
solvent.
[0129] As the solvent, well-known solvents can be used.
[0130] Specifically, examples thereof include a hydrocarbon-based
solvent such as hexane, octane, decane, toluene, xylene,
mesitylene, ethylbenzene, decalin, and 1-methylnaphthalene, a
ketone-based solvent such as acetone, methyl ethyl ketone, methyl
isobutyl ketone, or cyclohexanone, a halogenated hydrocarbon-based
solvent such as dichloromethane, chloroform, tetrachloromethane,
dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene,
dichlorobenzene, and chlorotoluene, an ester-based solvent such as
ethyl acetate, butyl acetate, and amyl acetate, an alcohol-based
solvent such as methanol, propanol, butanol, pentanol, hexanol,
cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene
glycol, an ether-based solvent such as dibutyl ether,
tetrahydrofuran, dioxane, and anisole, an amide-based solvent such
as N,N-dimethylformamide and N,N-dimethylacetamide, an imide-based
solvent such as 1-methyl-2-pyrrolidone and
1-methyl-2-imidazolidinone, a sulfoxide-based solvent such as
dimethylsulfoxide, and a nitrile-based solvent such as
acetonitrile.
[0131] The solvent may be used singly or two or more types thereof
may be used in combination.
[0132] Among these, a hydrocarbon-based solvent, a halogenated
hydrocarbon-based solvent, an aromatic solvent, an aromatic
heterocyclic solvent, and/or an ether-based solvent are preferable,
and toluene, xylene, mesitylene, tetralin, dichlorobenzene and
anisole are more preferable.
[0133] The boiling point of the solvent is preferably 100.degree.
C. or higher, in view of film formability. The boiling point of the
solvent is more preferably 100.degree. C. to 300.degree. C., even
more preferably 125.degree. C. to 250.degree. C., and particularly
preferably 150.degree. C. to 225.degree. C.
[0134] It is preferable that a boiling point of the solvent of
which the content is the greatest is 100.degree. C. or higher and,
it is more preferable that a boiling point of the entire solvent is
100.degree. C. or higher.
[0135] In a case where the solvent is contained, the content of the
specific organic semiconductor compound according to the
composition for forming the organic semiconductor film of the
present invention is preferably 0.05 to 50 mass %, more preferably
0.1 to 25 mass %, even more preferably 0.25 to 15 mass %,
particularly preferably 0.4 to 10 mass % with respect to the total
amount of the composition for forming the organic semiconductor
film. The content of the binder polymer is preferably 0.01 to 50
mass %, more preferably 0.05 to 25 mass %, and even more preferably
0.1 to 10 mass % with respect to the total amount of the
composition for forming the organic semiconductor film. If the
content is in the range above, the coating properties are
excellent, and the organic semiconductor film can be easily
formed.
[0136] The drying treatment in the removing step is a treatment
performed if necessary, and the optimal treatment conditions are
suitably selected according to the type of the specific organic
semiconductor compound used and the solvent. In view of further
improving mobility and heat stability of the obtained organic
semiconductor and improving productivity, a heating temperature is
preferably 30.degree. C. to 100.degree. C. and more preferably
40.degree. C. to 80.degree. C., and a heating time is preferably 10
to 300 minutes and more preferably 30 to 180 minutes.
[0137] A film thickness of the formed organic semiconductor layer
is not particularly limited. From the viewpoint of mobility and
heat stability of the obtained organic semiconductor, the film
thickness is preferably 10 to 500 nm and more preferably 30 to 200
nm.
[0138] The organic semiconductor element is not particularly
limited, but is preferably an organic semiconductor element having
2 to 5 terminals, and more preferably an organic semiconductor
element having 2 or 3 terminals.
[0139] It is preferable that the organic semiconductor element is
not a photoelectric conversion element.
[0140] The organic semiconductor element according to the present
invention is preferably a non-luminous organic semiconductor
element.
[0141] Examples of a 2-terminal element include a rectifier diode,
a constant voltage diode, a PIN diode, a Schottky barrier diode, a
surge protection diode, a diac, a varistor, a tunnel diode, and the
like.
[0142] Examples of a 3-terminal element include a bipolar
transistor, a Darlington transistor, a field effect transistor,
insulated gate bipolar transistor, a uni-junction transistor, a
static induction transistor, a gate turn-off thyristor, a triac, a
static induction thyristor, and the like.
[0143] Among these, a rectifier diode and transistors are
preferable, and a field effect transistor is more preferable.
[0144] An aspect of the organic thin film transistor of the present
invention will be described with reference to a drawing.
[0145] FIG. 1 is a schematic cross-sectional view of an aspect of
an organic semiconductor element (organic thin film transistor
(organic TFT)) of the present invention.
[0146] In FIG. 1, an organic thin film transistor 100 comprises a
substrate 10, a gate electrode 20 disposed on the substrate 10, a
gate insulating film 30 covering the gate electrode 20, a source
electrode 40 and a drain electrode 42 which contact a surface of
the gate insulating film 30 that is on the side opposite to the
gate electrode 20 side, an organic semiconductor film 50 covering a
surface of the gate insulating film 30 between the source electrode
40 and the drain electrode 42, and a sealing layer 60 covering each
member. The organic thin film transistor 100 is a bottom
gate-bottom contact type organic thin film transistor.
[0147] In FIG. 1, the organic semiconductor film 50 corresponds to
a film formed of the composition described above.
[0148] Hereinafter, the substrate, the gate electrode, the gate
insulating film, the source electrode, the drain electrode, the
organic semiconductor film, the sealing layer, and methods for
forming each of these will be specifically described.
[0149] <Substrate>
[0150] The substrate plays a role of supporting the gate electrode,
the source electrode, the drain electrode, and the like which will
be described later.
[0151] The type of the substrate is not particularly limited, and
examples thereof include a plastic substrate, a glass substrate, a
ceramic substrate, and the like. Among these, from the viewpoint of
applicability to each device and costs, a glass substrate or a
plastic substrate is preferable.
[0152] Examples of materials of the plastic substrate include a
thermosetting resin (for example, an epoxy resin, a phenol resin, a
polyimide resin, or a polyester resin (for example, polyethylene
terephthalate (PET) or polyethylene naphthalate (PEN)) and a
thermoplastic resin (for example, a phenoxy resin, a
polyethersulfone, polysulfone, or polyphenylene sulfone).
[0153] Examples of materials of the ceramic substrate include
alumina, aluminum nitride, zirconia, silicon, silicon nitride,
silicon carbide, and the like.
[0154] Examples of materials of the glass substrate include soda
lime glass, potash glass, borosilicate glass, quartz glass,
aluminosilicate glass, lead glass, and the like.
[0155] <Gate Electrode, Source Electrode, and Drain
Electrode>
[0156] Examples of materials of the gate electrode, the source
electrode, and the drain electrode include a metal such as gold
(Au), silver, aluminum (Al), copper, chromium, nickel, cobalt,
titanium, platinum, tantalum, magnesium, calcium, barium, or
sodium; a conductive oxide such as InO.sub.2, SnO.sub.2, or indium
tin oxide (ITO); a conductive polymer such as polyaniline,
polypyrrole, polythiophene, polyacetylene, or polydiacetylene; a
semiconductor such as silicon, germanium, or gallium arsenide; a
carbon material such as fullerene, carbon nanotubes, or graphite;
and the like. Among these, a metal is preferable, and silver and
aluminum are more preferable.
[0157] A thickness of each of the gate electrode, the source
electrode, and the drain electrode is not particularly limited, but
is preferably 20 to 200 nm.
[0158] A method of forming the gate electrode, the source
electrode, and the drain electrode is not particularly limited, but
examples thereof include a method of vacuum vapor-depositing or
sputtering an electrode material onto a substrate, a method of
coating a substrate with a composition for forming an electrode, a
method of printing a composition for forming an electrode onto a
substrate, and the like. Furthermore, in a case where the electrode
is patterned, examples of the patterning method include a
photolithography method; a printing method such as ink jet
printing, screen printing, offset printing, or relief printing; a
mask vapor deposition method; and the like.
[0159] <Gate Insulating Film>
[0160] Examples of materials of the gate insulating film include a
polymer such as polymethyl methacrylate, polystyrene,
polyvinylphenol, polyimide, polycarbonate, polyester,
polyvinylalcohol, polyvinyl acetate, polyurethane, polysulfone,
polybenzoxazole, polysilsesquioxane, an epoxy resin, or a phenol
resin; an oxide such as silicon dioxide, aluminum oxide, or
titanium oxide; a nitride such as silicon nitride; and the like.
Among these materials, in view of the compatibility with the
organic semiconductor film, a polymer is preferable.
[0161] In a case where a polymer is used as the material of the
gate insulating film, it is preferable to use a cross-linking agent
(for example, melamine) in combination. If the cross-linking agent
is used in combination, the polymer is cross-linked, and durability
of the formed gate insulating film is improved.
[0162] A film thickness of the gate insulating film is not
particularly limited, but is preferably 100 to 1,000 nm.
[0163] A method of forming the gate insulating film is not
particularly limited, but examples thereof include a method of
coating a substrate, on which the gate electrode is formed, with a
composition for forming a gate insulating film, a method of
vapor-depositing or sputtering the material of the gate insulating
film onto a substrate on which the gate electrode is formed, and
the like. A method of coating the aforementioned substrate with the
composition for forming a gate insulating film is not particularly
limited, and it is possible to use a known method (a bar coating
method, a spin coating method, a knife coating method, or a doctor
blade method).
[0164] In a case where the gate insulating film is formed by
coating the substrate with the composition for forming a gate
insulating film, for the purpose of removing the solvent, causing
cross-linking, or the like, the composition may be heated (baked)
after coating.
[0165] <Organic Semiconductor Film>
[0166] The organic semiconductor film according to the present
invention is a film formed with the composition for forming the
organic semiconductor film according to the present invention.
[0167] The method of forming an organic semiconductor film is not
particularly limited, and it is possible to form a desired organic
semiconductor film by applying the aforementioned composition to a
source electrode, a drain electrode, and a gate insulating film and
performing a dry treatment, if necessary.
[0168] <Binder Polymer Layer>
[0169] The organic semiconductor element of the present invention
preferably has a layer of the aforementioned binder polymer between
a layer containing the aforementioned organic semiconductor layer
and an insulating film, and more preferably has a layer of the
aforementioned binder polymer between the aforementioned organic
semiconductor layer and the gate insulating film. A film thickness
of the binder polymer layer is not particularly limited, but is
preferably 20 to 500 nm. The binder polymer layer should be a layer
containing the aforementioned polymer, and is preferably a layer
composed of the aforementioned binder polymer.
[0170] A method of forming the binder polymer layer is not
particularly limited, and a known method (a bar coating method, a
spin coating method, a knife coating method, a doctor blade method,
or an ink jet method) can be used.
[0171] In a case where the binder polymer layer is formed by
performing coating by using a composition for forming a binder
polymer layer, for the purpose of removing a solvent, causing
cross-linking, or the like, the composition may be heated (baked)
after coating.
[0172] <Sealing Layer>
[0173] From the viewpoint of durability, the organic semiconductor
element of the present invention preferably comprises a sealing
layer as an outermost layer. In the sealing layer, a known sealant
can be used.
[0174] A thickness of the sealing layer is not particularly
limited, but is preferably 0.2 to 10 .mu.m.
[0175] A method of forming the sealing layer is not particularly
limited, but examples thereof include a method of coating a
substrate, on which the gate electrode, the gate insulating film,
the source electrode, the drain electrode, and the organic
semiconductor film are formed, with a composition for forming a
sealing layer, and the like. Specific examples of the method of
coating the substrate with the composition for forming a sealing
layer are the same as the examples of the method of coating the
substrate with the composition for forming a gate insulating film.
In a case where the organic semiconductor film is formed by coating
the substrate with the composition for forming a sealing layer, for
the purpose of removing the solvent, causing cross-linking, or the
like, the composition may be heated (baked) after coating.
[0176] FIG. 2 is a schematic cross-sectional view of another aspect
of the organic semiconductor element (organic thin film transistor)
of the present invention.
[0177] In FIG. 2, an organic thin film transistor 200 comprises the
substrate 10, the gate electrode 20 disposed on the substrate 10,
the gate insulating film 30 covering the gate electrode 20, the
organic semiconductor film 50 disposed on the gate insulating film
30, the source electrode 40 and the drain electrode 42 disposed on
the organic semiconductor film 50, and the sealing layer 60
covering each member. Herein, the source electrode 40 and the drain
electrode 42 are formed using the aforementioned composition of the
present invention. The organic thin film transistor 200 is a bottom
gate-top contact type organic thin film transistor.
[0178] The substrate, the gate electrode, the gate insulating film,
the source electrode, the drain electrode, the organic
semiconductor film, and the sealing layer are as described
above.
[0179] In FIGS. 1 and 2, the aspects of the bottom gate-bottom
contact type organic thin film transistor and the bottom gate-top
contact type organic thin film transistor were specifically
described. However, the organic semiconductor element of the
present invention can also suitably used in a top gate-bottom
contact type organic thin film transistor and a top gate-top
contact type organic thin film transistor.
[0180] The organic thin film transistor described above can be
suitably used for electronic paper and a display device.
[0181] (Composition for Forming Organic Semiconductor Film)
[0182] The composition for forming the organic semiconductor film
according to the present invention contains the specific organic
semiconductor compound and a solvent.
[0183] The composition for forming the organic semiconductor film
according to the present invention preferably contains a binder
polymer.
[0184] The specific organic semiconductor compound, the binder
polymer, and the solvent in the composition for forming the organic
semiconductor film according to the present invention have the same
meanings as the specific organic semiconductor compound, the binder
polymer, and the solvent described above, and preferable aspects
thereof are also the same.
[0185] The composition for forming the organic semiconductor film
according to the present invention may include other component in
addition to the specific organic semiconductor compound and the
binder polymer.
[0186] As the component, well-known additives may be used.
[0187] The content of the component in addition to the specific
organic semiconductor compound and the binder polymer in the
composition for forming the organic semiconductor film according to
the present invention is preferably 10 mass % or less, more
preferably 5 mass % or less, even more preferably 1 mass % or less,
and particularly preferably 0.1 mass % or less with respect to the
total solid content of the composition for forming an organic
semiconductor film. If the content is in the range described above,
film formability is improved, and mobility and heat stability of
the obtained organic semiconductor are further improved. The solid
content is an amount of the components excluding the volatilizable
component such as the solvent.
[0188] The viscosity of the composition for forming the organic
semiconductor film according to the present invention is not
particularly limited. However, in view of excellent coating
properties, the viscosity is preferably 3 to 100 mPas, more
preferably 5 to 50 mPas, and even more preferably 9 to 40 mPas. The
viscosity according to the present invention refers to viscosity at
25.degree. C.
[0189] As a method of measuring the viscosity, a measuring method
in conformity of JIS Z8803 is preferable.
[0190] The method of manufacturing the composition for forming the
organic semiconductor film according to the present invention is
not particularly limited, and well-known methods can be applied.
For example, a desired composition can be obtained by adding a
specific amount of a specific organic semiconductor compound in the
solvent and applying a suitable stirring treatment. In a case where
the binder polymer is used, the specific organic semiconductor
compound and the binder polymer are simultaneously or sequentially
added, so as to suitably manufacture the composition.
[0191] (Organic Semiconductor Film)
[0192] The organic semiconductor film according to the present
invention contains the specific organic semiconductor compound.
[0193] The organic semiconductor film according to the present
invention preferably contains a binder polymer.
[0194] The specific organic semiconductor compound and the binder
polymer in the organic semiconductor film according to the present
invention have the same meanings as the specific organic
semiconductor compound, a polymer and an oligomer that can be
obtained by polymerizing the specific organic semiconductor
compound, and the binder polymer described above in the organic
semiconductor element according to the present invention, and
preferable aspects thereof are also the same.
[0195] The composition for forming the organic semiconductor film
according to the present invention may include other components in
addition to the specific organic semiconductor compound, a polymer
and an oligomer that can be obtained by polymerizing the specific
organic semiconductor compound, and the binder polymer.
[0196] As the component, well-known additives may be used.
[0197] The content of the component in addition to the specific
organic semiconductor compound, a polymer and an oligomer that can
be obtained by polymerizing the specific organic semiconductor
compound, and the binder polymer in the organic semiconductor film
according to the present invention preferably 10 mass % or less,
more preferably 5 mass % or less, even more preferably 1 mass % or
less, and particularly preferably 0.1 mass % or less with respect
to the total mass of the organic semiconductor film. If the content
is in the range above, film formability is improved, and mobility
and heat stability of the obtained organic semiconductor are
further improved. The solid content is an amount of components
other than the volatilizable components such as the solvent.
[0198] The film thickness of the organic semiconductor film
according to the present invention is not particularly limited.
However, in view of mobility and heat stability of the obtained
organic semiconductor, the film thickness is preferably 10 to 500
nm and more preferably 30 to 200 nm.
[0199] The organic semiconductor film according to the present
invention can be suitably used in the organic semiconductor
element, and can be particularly suitably used in the organic
transistor (organic thin film transistor).
[0200] The organic semiconductor film according to the present
invention can be suitably manufactured by using the composition for
forming the organic semiconductor film according to the present
invention.
EXAMPLES
[0201] Hereinafter, the present invention will be more specifically
described based on examples. The materials and the amount thereof
used, the proportion of the materials, the content and procedure of
treatments, and the like described in the following examples can be
suitably changed within a scope that does not depart from the gist
of the present invention. Accordingly, the scope of the present
invention is not limited to the following specific examples.
Herein, unless otherwise specified, "part" and "%" are based on
mass.
[0202] (Organic Semiconductor Compound)
[0203] E-1 to E-8 which were organic semiconductor compounds used
in the organic semiconductor layer were the same as E-1 to E-8
described as specific examples of the organic semiconductor
compound.
[0204] Structures of Exemplary Compounds C-1 to C-3 were provided
below.
##STR00020##
[0205] <Synthesis of Compounds>
[0206] Compound E-1 was synthesized in a synthesis scheme
below.
[0207] Specifically, with reference to Macromol., 2008, 41, 7287.,
Synthesis Intermediate IM was synthesized.
[0208] Synthesis Intermediate IM (92 mg, 0.2 mmol),
2,5-bis(trimethylstannyl)-3,6-didodecylthieno[3,2-b]thiophene (160
mg, 0.2 mmol), tri(o-tolyl) phosphine (4.9 mg, 0.016 mmol),
tris(dibenzylideneacetone) dipalladium (3.7 mg, 0.004 mmol), and
dehydrated chlorobenzene (20 mL) were mixed and were stirred at
130.degree. C. for 72 hours under a nitrogen atmosphere. After the
reaction solution was cooled to room temperature, 100 mL of
methanol and 8 mL of concentrated hydrochloric acid were added and
were stirred for 16 hours. The precipitated solid content was
filtrated and washed with methanol, Soxhlet extraction was
sequentially performed with ethanol, ethyl acetate, and chloroform,
and soluble impurities were removed. Soxhlet extraction was
performed with chlorobenzene, the solution was concentrated under
reduced pressure, methanol was added, and the precipitated solid
was filtered and washed with methanol, so as to obtain 70 mg of
Compound E-1 (yield: 45%).
[0209] Compounds E-2 to E-8 were also synthesized in conformity
with Compound E-1.
##STR00021##
[0210] Comparative Compounds C-1 and C-2 were compounds disclosed
in Examples 2 and 12 of JP2007-516315A.
[0211] Comparative Compound C-3 was a compound disclosed in
JP2014-507488A.
[0212] It was checked that in all of Compounds E-1 to E-8 and
Exemplary Compounds C-1 to C-3, the purity (absorption intensity
area ratio of 254 nm) was 99.8% or greater by high performance
liquid chromatography (manufactured by Tosoh Corporation, TSKgel
ODS-100Z).
[0213] <Reagent Used>
[0214] 2-Acetyl-5-bromothiophene used in the synthesis of Compound
E-1 was obtained from Tokyo Chemical Industry Co., Ltd.
[0215]
2,5-Bis(trimethylstannyl)-3,6-didodecylthieno[3,2-b]thiophene was
synthesized by the synthesis scheme below with reference to
WO2005/111045A and J. Polym. Sci. Part A Polym. Chem., 2013, 51,
424. by using 3,6-dibromothieno[3,2-b]thiophene (manufactured by
Tokyo Chemical Industry Co., Ltd.) and N-dodecyl zinc bromide
(manufactured by Alfa Aesar) as starting materials.
##STR00022##
[0216] <Binder Polymer>
[0217] A polymer used as a binder polymer is provided below.
[0218] P.alpha.MS: Poly-.alpha.-methylstyrene, weight-average
molecular weight: 437,000, manufactured by Sigma-Aldrich Co.
LLC.
[0219] PTAA: Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine],
number-average molecular weight: 7,000 to 10,000, manufactured by
Sigma-Aldrich Co. LLC.
[0220] PCPDTBT: Poly[2,6-(4,4-bis(2-ethylhexyl)-4H
cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)],
weight-average molecular weight: 7,000 to 20,000, manufactured by
Sigma-Aldrich Co. LLC.
[0221] <Preparing Coating Liquid for Forming Organic
Semiconductor Film>
[0222] An organic semiconductor compound (0.5 mass %)/a binder
polymer (concentration disclosed in Table 1)/anisole (boiling
point: 154.degree. C.) presented in Table 1 was weighed in glass
vial, stirring and mixing was performed for 10 minutes with a mix
rotor (manufactured by As One Corporation), and filtration was
performed with a 0.5 .mu.m membrane filter, so as to obtain the
coating liquid for forming the organic semiconductor film (the
composition for forming the organic semiconductor film). In Table
1, "-" presented in a binder polymer indicates that the binder
polymer was not included.
[0223] In Table 1, the concentration of the binder polymer
disclosed in the brackets was mass % in the coating liquid.
[0224] <Manufacturing of TFT Element>
[0225] Al that became a gate electrode was vapor-deposited on the
glass substrate (EAGLE XG: manufactured by Corning Incorporated)
(Thickness: 50 nm). Spin coating was performed with a composition
(solution (concentration of solid contents: 2 mass %) of propylene
glycol monomethyl ether acetate (PGMEA) of
polyvinylphenol/melamine=1 part by mass/1 part by mass (w/w)) for
forming a gate insulating film, and the gate insulating film having
a film thickness of 400 nm was formed by performing baking at
150.degree. C. for 60 minutes. Shapes of source electrodes and
drain electrodes (channel length: 40 .mu.m, channel width: 200
.mu.m) were drawn thereon, with silver ink (H-1, manufactured by
Mitsubishi Materials Corporation) by using an inkjet device
DMP-2831 (manufactured by Fujifilm Corporation). Thereafter, baking
was performed in an oven at 180.degree. C. for 30 minutes,
sintering was performed, and source electrodes and drain electrodes
were formed, so as to obtain an element substrate for TFT
characteristic evaluation.
[0226] In a nitrogen glove box, spin coating was performed on the
element substrate for TFT characteristic evaluation with the
coating liquid for forming the respective organic semiconductor
films (for 10 seconds at 500 rpm and for 30 seconds at 1,000 rpm),
and drying was performed on a hot plate at 200.degree. C. for 10
minutes, so as to form an organic semiconductor layer such that a
bottom gate bottom contact-type organic TFT element was
obtained.
[0227] <Characteristic Evaluation>
[0228] The following performance evaluation was carried out under
the atmosphere by using a semiconductor characteristic evaluation
device B2900A (manufactured by Agilent Technologies Japan,
Ltd.).
[0229] (a) Carrier Mobility
[0230] Carrier mobility .mu. was calculated by applying a voltage
of -60V between source electrodes-drain electrodes of the
respective organic TFT elements, changing gate voltages in the
range of +10 V to -60 V, and using an equation below indicating a
drain current I.sub.d.
I.sub.d=(w/2L).mu.C.sub.i(V.sub.g-V.sub.th).sup.2
[0231] In the equation, L represents a gate length, w represents a
gate width, C.sub.i represents capacity per unit area of an
insulating layer, V.sub.g represents a gate voltage, and V.sub.th
represents a threshold voltage.
[0232] As carrier mobility .mu. is higher, the carrier mobility
.mu. is more preferable. In practice the carrier mobility .mu. is
preferably 8.0.times.10.sup.-3 cm.sup.2/Vs or greater, more
preferably 1.0.times.10.sup.-2 cm.sup.2/Vs or greater, and even
more preferably 1.0.times.10.sup.-1 cm.sup.2/Vs or greater. If the
mobility was lower than 1.0.times.10.sup.-5 cm.sup.2/Vs,
characteristics were too small, it is presented that
"<1.0.times.10.sup.-5" in the table, and thus the evaluation was
not performed.
[0233] (b) Temporal Stability Under High Humidity
[0234] In a case where the respective manufactured organic thin
film transistor elements were stored at 25.degree. C., under the
humidity of 80% RH for 24 hours and carrier mobility was measured,
the carrier mobility maintenance ratio was evaluated in the
following four stages and was set as an index of temporal stability
under high humidity. As this value is greater, stability under high
humidity is high. In practice, A or B was preferable, and A was
more preferable.
[0235] Carrier mobility maintenance ratio after storage under high
humidity (%)=mobility (after storage under high humidity)/mobility
(before storage under high humidity)
[0236] A: 80% or greater
[0237] B: 60% or greater and less than 80%
[0238] C: 40% or greater and less than 60%
[0239] D: Less than 40%
TABLE-US-00001 TABLE 1 Temporal stability Binder Carrier under
Element Organic polymer mobility high Number semiconductor Mn Mw
(mass %) (cm.sup.2/Vs) humidity Example 1 Element 1-1 Compound E-1
100,000 440,000 -- 7.3 .times. 10.sup.-2 A Example 2 Element 1-2
Compound E-1 100,000 440,000 P.alpha.MS 7.8 .times. 10.sup.-2 A
(0.5) Example 3 Element 1-3 Compound E-2 25,000 97,000 -- 8.5
.times. 10.sup.-2 A Example 4 Element 1-4 Compound E-3 45,000
160,000 -- 9.1 .times. 10.sup.-2 A Example 5 Element 1-5 Compound
E-4 82,000 280,000 -- 2.3 .times. 10.sup.-1 A Example 6 Element 1-6
Compound E-4 82,000 280,000 PTAA 2.4 .times. 10.sup.-1 A (0.125)
Example 7 Element 1-7 Compound E-5 65,000 250,000 -- 8.8 .times.
10.sup.-2 A Example 8 Element 1-8 Compound E-5 65,000 250,000
PCPDTBT 9.1 .times. 10.sup.-2 A (0.25) Example 9 Element 1-9
Compound E-6 87,000 320,000 -- 2.5 .times. 10.sup.-2 B Example 10
Element 1-10 Compound E-7 70,000 310,000 -- 1.1 .times. 10.sup.-2 A
Example 11 Element 1-11 Compound E-8 15,000 57,000 -- 9.3 .times.
10.sup.-3 A Comparative Element 1-12 Comparative 10,000 31,000 --
1.5 .times. 10.sup.-5 D Example 1 Compound 1 Comparative Element
1-13 Comparative 400 1,250 -- <1.0 .times. 10.sup.-5 -- Example
2 Compound 2 Comparative Element 1-14 Comparative 68,000 190,000 --
4.1 .times. 10.sup.-3 D Example 3 Compound 3
EXPLANATION OF REFERENCES
[0240] 10: substrate [0241] 20: gate electrode [0242] 30: gate
insulating film [0243] 40: source electrode [0244] 42: drain
electrode [0245] 50: organic semiconductor film [0246] 60: sealing
layer [0247] 100, 200: organic thin film transistor
* * * * *